US9296895B2 - Self-healing polymeric materials via unsaturated polyester resin chemistry - Google Patents

Self-healing polymeric materials via unsaturated polyester resin chemistry Download PDF

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US9296895B2
US9296895B2 US14/303,494 US201414303494A US9296895B2 US 9296895 B2 US9296895 B2 US 9296895B2 US 201414303494 A US201414303494 A US 201414303494A US 9296895 B2 US9296895 B2 US 9296895B2
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healing
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resin
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Gerald O. Wilson
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No Corrosion LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
    • B29C73/16—Auto-repairing or self-sealing arrangements or agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
    • B29C73/16—Auto-repairing or self-sealing arrangements or agents
    • B29C73/22—Auto-repairing or self-sealing arrangements or agents the article containing elements including a sealing composition, e.g. powder being liberated when the article is damaged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/241—Preventing premature crosslinking by physical separation of components, e.g. encapsulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/08—Polyesters modified with higher fatty oils or their acids, or with resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/08—Polyesters modified with higher fatty oils or their acids, or with resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine

Definitions

  • Embodiments herein relate to self-healing materials, particularly self-healing materials based on unsaturated multi-functional resins capable of oxygen-initiated cross-linking.
  • the failure of polymeric materials can have significant consequences.
  • the failure of a coating due to a significant traumatic event or mechanical damage due to a more gradual decline as a result of the coating's environment may lead to exposure of the underlying substrate to the environment. Once exposed, a substrate may degrade through corrosion, in the case of metal substrates, or through other decomposition reactions, in the case of non-metal substrates.
  • the failure of coatings, polymerized resins, adhesives, sealants, and composites may necessitate costly repairs and the sidelining of parts, equipment, or facilities comprised of these materials.
  • increasingly expensive starting materials from petroleum stocks, as well as the need for the minimization of environmental impact all benefit from the use of longer-lasting materials. Materials that can repair themselves when they are damaged will last longer in their specific applications.
  • FIG. 1 illustrates the chemical synthesis of an alkyd resin from linoleic acid and phthalic anhydride, in accordance with various embodiments
  • FIGS. 2A-2C depict a schematic diagram illustrating self-healing via cross-linking of unsaturated functional groups of an alkyd resin, including the microencapsulated healing agent formulation ( FIG. 2A ), the release of the resin at the damage site ( FIG. 2B ), and the cross-linking of the resin at the damage site ( FIG. 2C ), in accordance with various embodiments;
  • FIG. 3 is a schematic diagram illustrating a one-capsule system, in accordance with various embodiments.
  • FIG. 4 illustrates the chemical structure of an example of a representative resin used in several coating performance tests, in accordance with various embodiments
  • FIGS. 5A-5C illustrate self-healing performance observed in a polyurea coating
  • FIG. 5A shows the results of a test with a control sample, which was an un-pigmented polyurea coating
  • FIG. 5B illustrates the results of a test with a self-healing sample, which contained 20 wt % of microcapsules containing ethyl phenyl acetate and an alkyd resin with epoxy end groups (the microcapsule additives are referred to herein as Series 3 (S3))
  • FIG. 5C is a graph illustrating the degree of corrosion creep observed with two different sizes of scribes, in accordance with various embodiments;
  • FIGS. 6A-6E illustrate self-healing performance in a polyethylene powder coating, where self-healing of scribes with 3 different widths (46 microns, 186 microns, and 500 microns) was evaluated, and wherein FIG. 6A illustrates the results of a test with a control sample, FIG. 6B illustrates the results of a test with a sample containing 20 wt % of microcapsules containing ethyl phenyl acetate and an alkyd resin with epoxy end groups, FIG. 6C is a graph illustrating the degree of corrosion creep observed with a 46 micron scribe, FIG. 6D is a graph illustrating the degree of corrosion creep observed with a 186 micron scribe, and FIG. 6E is a graph illustrating the degree of corrosion creep observed with a 500 micron scribe, in accordance with various embodiments;
  • FIGS. 7A-7C depict a schematic diagram illustrating self-healing via cross-linking of unsaturated functional groups of an alkyd resin, including the microencapsulated healing agent formulation ( FIG. 7A ), the release of the resin at the damage site ( FIG. 7B ), and the cross-linking of the resin at the damage site, as well as the formation of covalent linkages, non-covalent linkages, or both covalent and non-covalent linkages with the matrix ( FIG. 7C ), in accordance with various embodiments;
  • FIGS. 8A-8C illustrate the self-healing performance of two versions of an epoxy coating applied to CRS panels, wherein FIG. 8A illustrates a control sample, which was coated with a commercially available epoxy primer, FIG. 8B illustrates a self-healing sample, which was coated with the same commercially available epoxy primer, to which 5 wt % of microcapsules containing ethyl phenyl acetate and an alkyd resin with epoxy end groups had been added, and FIG. 8C is a graph illustrating the degree of corrosion creep observed with two different sizes of scribes, in accordance with various embodiments;
  • FIG. 9 is a schematic diagram illustrating an example of a standard dual-capsule system, in accordance with various embodiments.
  • FIG. 10 illustrates a schematic diagram illustrating an example of a hybrid dual-capsule system, in accordance with various embodiments.
  • Coupled may mean that two or more elements are in direct physical or electrical contact. However, “coupled” may also mean that two or more elements are not in direct contact with each other, but yet still cooperate or interact with each other.
  • a phrase in the form “A/B” or in the form “A and/or B” means (A), (B), or (A and B).
  • a phrase in the form “at least one of A, B, and C” means (A), (B), (C), (A and B), (A and C), (B and C), or (A, B and C).
  • a phrase in the form “(A)B” means (B) or (AB) that is, A is an optional element.
  • self-healing materials which are smart materials that are capable of repairing themselves without any external intervention when they are damaged.
  • some or all of the self-healing materials may be microencapsulated, and damage to a matrix containing the microcapsules may rupture the microcapsules and cause the healing materials to be released into the site of damage, where they may polymerize and restore the functional capabilities of the matrix.
  • matrix refers to any material that includes a plurality of microcapsules.
  • FIG. 1 illustrates the chemical synthesis of an alkyd resin from linoleic acid and phthalic anhydride.
  • alkyd resins such as the illustrated resin may be used as a self-healing agent in a self-healing polymer system.
  • various self-healing systems may take advantage of the ability of unsaturated functional groups, such as those present in fatty acids (labeled “A” in FIG. 1 ), to cross-link in the presence of oxygen.
  • unsaturated functional groups such as those present in fatty acids (labeled “A” in FIG. 1 )
  • a tri-functional alcohol such as glycerol
  • an acid such as anhydride functionality
  • the disclosed self-healing materials may be configured as a one-capsule system, whereas other embodiments may take the form of a two-capsule system.
  • a healing material comprising a resin, such as an alkyd resin
  • a resin such as an alkyd resin
  • the polar solvent may have a range of properties that renders it suitable for encapsulation and stabilization of the resin to prevent premature cross-linking of the resin.
  • FIG. 2A-2C which depict self-healing via cross-linking of unsaturated functional groups of an alkyd resin, including the microencapsulated healing agent formulation ( FIG. 2A ), the release of the resin at the damage site ( FIG. 2B ), and the cross-linking of the resin at the damage site ( FIG. 2C ).
  • the non-polar solvents may be common solvents such as xylene ethyl benzene or low polarity acetates
  • the polar solvents generally possess a set of properties that enable microencapsulation and stabilization of the resin.
  • the polar solvent may maintain a polar environment within the capsules, thus preventing premature cross-linking of the resin (e.g., due to antioxidation).
  • the solvent also may have a dielectric constant of ⁇ 5.0, and may have a high enough boiling point to maintain high thermal stability for the system as a whole, for example ⁇ 225° C. in various embodiments.
  • the polar solvent may have a low enough vapor pressure to prevent premature evaporation, which could compromise the polar environment and potentially lead to premature cross-linking of the resin in the healing agent formulation. In some embodiments, a vapor pressure of ⁇ 0.5 mm Hg at 20° C. also is desirable. In various embodiments, the polar solvent also is insoluble in water for facile incorporation into a hydrophobic healing agent formulation and encapsulation, and generally the polar solvent also has low toxicity, with LD 50 (oral, rat) values ⁇ 3000 mg/kg.
  • solvents that meet these criteria include, but are not limited to ethyl phenyl acetate (CAS #: 101-97-3), phenyl ethyl acetate (CAS #: 103-45-7), and phenyl ethyl phenyl acetate (CAS #: 102-20-5).
  • the characteristics of the polar aprotic solvent may be selected in order to achieve the desired kinetics for the self-healing process. As described above, in some embodiments, the characteristics of the polar aprotic solvent may be optimized to prevent premature cross-linking of the healing agent that would render it unavailable during a healing event. However, in other embodiments, the formulation may be customized in order to increase or decrease the healing agent reaction rate as desired. For example, because the reaction of the healing agent depends on the cross-linking of the unsaturated groups, which will not readily occur in the presence of the polar aprotic solvent, in some embodiments, the concentration of the polar aprotic solvent in the healing agent formulation may be adjusted to tune the healing kinetics of a self-healing system.
  • Table 1 shows an example of the effect of decreasing the concentration of a polar aprotic solvent (ethyl phenyl acetate in this case) on the gelation and cure times of the healing agent formulation.
  • a polar aprotic solvent ethyl phenyl acetate in this case
  • FIG. 3 is a schematic diagram illustrating a one-capsule system, in accordance with various embodiments. Whether the application is a coating, sealant, adhesive, thermosetting composite, thermoplastic composite, or some other polymeric matrix material, microcapsules may be embedded in the material prior to use in the specific application.
  • FIG. 4 illustrates the chemical structure of an example of a representative resin used in coating performance tests, in accordance with various embodiments.
  • the cross-linking of the unsaturated groups in the fatty acid chain leads to the formation of a cured polymer that restores the barrier property of the coating.
  • FIGS. 5A-5C illustrate self-healing performance observed in a polyurea coating.
  • FIG. 5A illustrates the results of a test with a control sample, which was an un-pigmented polyurea coating
  • FIG. 5B illustrates the results of a test with a self-healing sample, which contained 20 wt % of microcapsules containing ethyl phenyl acetate and an alkyd resin with epoxy end groups (the microcapsule additives are referred to as Series 3 (S3))
  • FIG. 5C is a graph illustrating the degree of corrosion creep observed with two different sizes of scribes, in accordance with various embodiments. For the example illustrated in FIG.
  • the microcapsules were mixed into the coating formulation prior to application on the substrate.
  • the coating samples were prepared by drawing down the coating onto the desired substrate using a draw down bar, although similar results have been observed using conventional and airless spray equipment. After application of the coating, the sample was allowed to cure for 24 hours, after which it was intentionally damaged using 186 and 500-micron scribe tools, respectively.
  • the samples were then allowed to heal at room temperature for 24 hours and then put into a salt fog, in which they were exposed to conditions specified by ASTM B117 for 1000 hours (ASTM Standard B117-11, 2003, “Standard Practice for Operating Salt Spray (Fog) Apparatus,” ASTM International, West Conshohocken, Pa., www.astm.org). After exposure to the salt fog, the amount of corrosion creep from the scribe was measured in mm.
  • FIGS. 5A and 5B show two versions of an un-pigmented polyurea coating applied to cold-rolled steel (CRS) substrates.
  • the control sample ( FIG. 5A ) was coated with the standard un-pigmented coating, while the self-healing sample ( FIG. 5B ) contained 20 wt % of microcapsules containing a formulation comprised of an alkyd resin such as that shown in FIG. 4 , and a polar solvent meeting the criteria described above such as ethyl phenyl acetate.
  • a polar solvent meeting the criteria described above such as ethyl phenyl acetate.
  • the control sample after exposure to ASTM B117, the control sample exhibited significant visible corrosion creep from scribe, while the self-healing exhibited minimal (in the case of the 500 micron scribe damage) to hardly any corrosion creep from scribe (in the case of the 186 micron scribe damage). Similar results also were observed for a range of coating and matrix chemistries including epoxies, polyurethanes, alkyds, epoxy vinyl esters, silicones, and other liquid coating chemistries.
  • FIGS. 6A-6E illustrate self-healing performance in a polyethylene powder coating, wherein self-healing of scribes with 3 different widths (46 microns, 186 microns and 500 microns) was evaluated; wherein FIG. 6A illustrates the results of a test with the control sample, FIG. 6B illustrates the results of a test with a sample containing 20 wt % of microcapsules containing ethyl phenyl acetate and an alkyd resin with epoxy end groups, FIG. 6C is a graph illustrating the degree of corrosion creep observed with a 46 micron scribe, FIG. 6D is a graph illustrating the degree of corrosion creep observed with a 186 micron scribe, and FIG.
  • 6E is a graph illustrating the degree of corrosion creep observed with a 500 micron scribe, in accordance with various embodiments.
  • powder coatings which are cured when polymeric particles heated above their melting point, melt and flow to form a uniform coating, are not easily repaired in service with the same kind of coating. This is due to the fact that powder-coated parts are often cured in large ovens that are not feasible to use in service. When these coatings are used for protection of the underlying asset from corrosion, the inability to properly repair them in service when they are damaged is of significant concern.
  • FIGS. 6A-6E spray-dried microcapsules were mixed into dry powder coating formulations to form dry blends that were then applied to CRS substrates via an electrostatic spray-gun or a fluidized bed.
  • the control sample exhibited significant corrosion creep from scribe after exposure to ASTM B117 conditions for 1000 hours (see, e.g., FIG. 6A )
  • the self-healing samples exhibited minimal corrosion creep from scribe (see, e.g., FIG. 6B ).
  • FIGS. 6C-6E the control sample exhibited significant visible corrosion creep from scribe, while the self-healing exhibited minimal (in the case of the 500 micron scribe damage, FIG.
  • matrix adhesion may be improved via functional group matching.
  • self-healing performance may be improved and thereby the concentration of the microencapsulated self-healing additive may be lowered by taking advantage of telechelic groups in the resin.
  • functional group matching may be used with an alkyd resin with telechelic epoxy functional groups as illustrated in FIG. 4 . For instance, when a self-healing material is formulated as described above, and a resin such as that shown in FIG. 4 is released into the site of damage during a healing event, the epoxy group will cross-link with residual epoxy groups and epoxy curing agents present in the matrix.
  • the result is a polymerized healing agent that is covalently bonded to the matrix in addition to other non-covalent interactions that are likely to be present (see, e.g., FIG. 6 ).
  • This improved adhesion to the matrix may lead to improved self-healing performance at lower concentrations of the healing agent.
  • FIG. 4 uses an alkyd resin with telechelic epoxy functional groups
  • other embodiments may use an alkyd resin that includes telechelic end groups that may cross-link with other complementary residual reactive groups such as isocyanates, polyols, vinyl-terminated silanes, vinyl and other unsaturated groups.
  • FIGS. 7A-7C depict a schematic diagram illustrating improved adhesion to the matrix with a self-healing via cross-linking of unsaturated functional groups of an alkyd resin, including the microencapsulated healing agent formulation ( FIG. 7A ), the release of the resin at the damage site ( FIG.
  • FIGS. 8A-8C illustrate the self-healing performance of two versions of an epoxy coating applied to CRS panels, wherein FIG. 8A illustrates a control sample, which was coated with a commercially available epoxy primer, FIG. 8B illustrates a self-healing sample, which was coated with the same commercially available epoxy primer, to which 5 wt % of microcapsules containing ethyl phenyl acetate and an alkyd resin with epoxy end groups had been added, and FIG. 8C is a graph illustrating the degree of corrosion creep observed with two different sizes of scribes, in accordance with various embodiments. As exhibited in FIG. 8C , while corrosion creep from the initial 186 and 500-micron scribes is significant for the control samples after exposure to conditions specified by ASTM B117, corrosion from similar scribes is in the self-healing sample is limited.
  • Similar self-healing systems may be used in which the telechelic groups of the multifunctional resin (e.g., B-groups in FIG. 4 ) are functional groups, such as isocyantes or polyols for cross-linking with polyurethane matrices, silanol or vinyl terminated silanes for cross-linking with silicone-based matrices, vinyl groups for cross-linking with vinyl esters etc.
  • Various unsaturated fatty acids e.g., palmitoleic acid, oleic acid, docosahexaenoic acid
  • other unsaturated functional groups e.g., A-groups in FIG. 4
  • A-groups in FIG. 4 may be used in the design of self-healing systems based on this concept.
  • the core tri-functional alcohol on which the multi-functional resin or monomer is based can be any tri-functional alcohol such as glycerol, a trifunctional silanol or any other tri-functional alcohol that may include other functional groups such as fluorinated functional groups or other reactive functional groups such as epoxy, vinyl or isocyanate groups as additional points for cross-linking.
  • FIG. 9 is a schematic diagram illustrating an example of a standard dual-capsule system, in accordance with various embodiments.
  • two varieties of microcapsules may be embedded into the matrix.
  • the first variety of microcapsules may contain a healing agent formulated as described above for a one-capsule system (Capsule A, FIG. 9 ).
  • the second variety of microcapsules may contain a catalyst, typically a metallic salt or complex, which is commonly referred to as a drier when the resin or monomer is an alkyd (Capsule B, FIG. 9 ).
  • a catalyst typically a metallic salt or complex
  • metal complexes that can be used either by themselves or in combination with others include primary driers based on cobalt, manganese, iron, cerium, and vanadium. These driers can be used in concert with secondary driers based on zirconium, bismuth, barium, and aluminum complexes and or auxiliary driers based on calcium, zinc, lithium and potassium complexes, to name a few examples.
  • the non-polar solvent in the capsule containing the resin may be used as the medium for delivery of the catalyst (Capsule B).
  • FIG. 10 illustrates a schematic diagram illustrating an example of such a hybrid dual-capsule system, in accordance with various embodiments.
  • Capsule B in the standard dual-capsule system improves the rate and degree of cross-linking of the unsaturated groups (A-groups)
  • the inclusion of a curing agent for the telechelic group improves efficiency of conversion of these groups and thus cross-linking with the matrix.
  • microencapsulate healing agent formulations in microcapsules comprised of polymeric shell walls various shell walls can be used for the compartmentalization of healing agents including urea-formaldehyde, polyurethane, and combinations of the two.
  • Resulting microcapsules may be incorporated into a formulation in a wet final form (such as a slurry or wet cake), which might contain moisture at 15 wt % and greater or in a dry final form, which typically contains moisture at 2 wt % or less. All microcapsules may be produced at a range of 1 micron or greater, but in various embodiments, size scales for the applications discussed above may be between 5 and 100 microns.
  • self-healing materials based on the present system may be comprised of microcapsules at concentrations as low as 1 wt % and as high as 20 wt %.

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EP3487636A4 (en) * 2016-07-21 2020-03-25 Autonomic Materials, Inc. DETACHABLE, SELF-HEALING COATINGS AND COLORS FOR POROUS SUBSTRATES

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BR112015031284B1 (pt) 2020-06-23
JP2016521802A (ja) 2016-07-25
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US20140371362A1 (en) 2014-12-18
BR112015031284A2 (pt) 2017-07-25

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